将实验室烧制的无机快离子导体盐Li1.3 Al0.3Ti1.7(PO4)3、PEO与LiClO4按照EO/Li=8,两种锂盐含量为变量进行复合,通过溶液浇注法制备得到PEO-LiClO4-Li1.3Al0.3Ti1.7(PO4)3复合聚合物电解质膜,以示差扫描热分析法(DSC)与电化学阻抗(EIS)测试其性能.DSC测试结果表明:按照EO/Li=8将Li1.3Al0.3Ti17(PO4)3、LiClO4与PEO复合的聚合物电解质中PEO的结晶度由50.34%下降到4.36%～28.53%.室温下该聚合物电解质所有试样的阻抗谱图在高频区呈现为压缩的半圆,在低频区为一条倾斜的直线,而在较高温度时,阻抗谱图主要为一条倾斜的直线.复合聚合物电解质PEO-LiClO4-Li1.3Al0.3Ti17(PO4)3的离子电导率遵从Ar-rhenius关系,在Li1.3Al03Ti1.7(PO4)3质量分数达到15%时,活化能最低,即4.494425 eV,此时电导率值最佳,373 K时为1.161×10-3S/cm和298 K时为7.985×10-6S/cm.
参考文献
| [1] | [l]Wright P V. Electrical conductivity in ionic complexes of poly(Ethyleneoxide) [J]. BrPolym J, 1975, 7(5): 327-341. |
| [2] | Armand M B, Chabagno J M, Duclot M J. In: Vashishta P, Mundy J N, Shenoy G K, eds. Fast ion transport in solids [M], New York: Elsevier Press Inc, 1979. 131-135. |
| [3] | Kumar B, Rodrigues S J, Koka S. The crystalline to amorphous transition in PEO-based composite electrolytes: Role of lithium salts [J]. Electrochimica Acta, 2002, 47 (25):4125-4131. |
| [4] | Berthier C, Gorecki W, Armand M B, et al. Microscopic investigation of ionic conductivity in alkali metal salts-poly (Ethylene oxide) adducts [J]. Solid State Ionics, 1983, 11(1): 91-95. |
| [5] | MacGlashan G S, Andreev Y G, Bruce P G. Structure of the polymer electrolyte poly(Ethylene oxide) 6: LiAsF6 [J].Nature, 1999, 398(6730): 792-793. |
| [6] | Gadjourova Z, Andreev Y G, Tunstall D P, et al. Ionic conductivity in crystalline polymer electrolytes [J]. Nature,2001, 412(6846): 520-523. |
| [7] | Sorensen P R, Jacobson T. Conductivity, charge transfer and transport number-an ac-investigation of the polymer electrolyte LiSCN-poly (ethyleneoxide) [J]. Electrochim Acta,1982, 27(12): 1671-1675. |
| [8] | Appetecchi G B, Henderson W, Villano P, et al. PEO-LiN (SO2CF2CF3)2 polymer electrolytes (Ⅰ): XRD, DSC, and ionic conductivity characterization [J]. Journal of the Electrochemical Society, 2001, 148(10): A1171-A1178. |
| [9] | Dygas J R, Misztal-Faraj B, Florjanczyk Z, et al. Effects of inhomogeneity on ionic conductivity and relaxations in PEO and PEO-salt complexes [J]. Solid State Ionics, 2003, 157(1-4): 249-256. |
| [10] | Croce F, Appetecchi G B, Persl L. Nanocomposite polymer electrolytes for lithium batteries [J]. Nature, 1998, 394(6692): 456-458. |
| [11] | Ji K S, Moon H S, Kim J W, et al. Role of functional nano-sized inorganic fillers in poly(Ethylene)oxide-based polymer electrolytes [J]. Journal of Power Sources, 2003,117(1-2): 124-130. |
| [12] | Dissanayake M A K L, Jayathilaka P A R D, Bokalawala R S P. Effect of concentration and grain size of alumina filler on the ionic conductivity enhancement of the (PEO)9LiCF3SO3 :Al2O3 composite polymer electrolyte [J]. Journal of Power Sources, 2003, 119-121: 409-414. |
| [13] | McCormick D T, Fordham Z W, Smith J, et al. Polymer molecular weight and chain transfer during the photopolymerization of an aliphatic monoacrylate in a smectic liquid crystal [J]. Polymer, 2003, 44: 2751-3759. |
| [14] | Suzuki T, Yoshida K, Uematsu K, et al. Stabilization of superionic conduction phase in Li3Sc2 (PO4)3 [J]. Solid State Ionics, 1997, 104(1-2): 27-33. |
| [15] | Bykov A B, Chirkin A P, Demyanets L N, etal. Superionic conductors Li3M2 (PO4)3 (M= Fe, Sc, Cr): Synthesis,structure and electrophysical properties [J]. Solid State Ionics, 1990, 38(1-2): 31-52. |
| [16] | Suzuki T, Yoshida K, Uematsu K, et al. Structure refinement of lithium ion conductors Li3Sc2 (PO4)3 and Li3-2x (Sc1-2xMx)2(PO4)3(M=Ti, Zr) with x=0. 10 by neutron diffraction [J]. SolidState Ionics, 1998, 113-115: 89-96. |
| [17] | Aono H, Sugimoto E, Sadaoka Y, etal. Ionic conductivity of solid electrolytes based on lithium titanium phosphate [J].J ElectrochemSoc, 1990, 137(4): 1023-1027. |
| [18] | Fu J. Fast Li+ ion conduction in Li2O-(Al2O3 Ga2O3)-TiO2-P2O5 glass-ceramics [J]. J MaterSci, 1998, 33(6): 1549-1553. |
| [19] | Leo C J, Subba Rao G V, Chowdari B V R. Studies on plasticized PEO-lithium triflate-ceramic filler composite electrolyte system [J]. Solid State Ionics, 2002, 148(1-2):159-171. |
| [20] | Sreekanth T, Jaipal Reddy M, Subramanyam S, et al. Ion conducting polymer electrolyte films based on (PEO+KNO3)system and its application as an electrochemical cell [J]. MaterSciEng, 1999, B64(2): 107-112. |
| [21] | Sreekanth T, Jaipal Reddy M, Subramanyam S, et al. Ion conducting polymer electrolyte based on poly (Ethylene oxide) complexed with NaNO3 salt-application as an electrochemical cell [J]. J Power Sources, 1999, 79(1): 105-110. |
| [22] | Druger S D, Nitzam A, Ratner M A. Dynamic bond percolation theory: A microscopic model for diffusion in dynamically disordered systems (Ⅰ): Definition and one-dimensional case [J]. J Chem Phys, 1983, 79(6): 3133-3142. |
| [23] | Druger S D, Nitzam A, Ratner M A. Generalized hopping model for frequency-dependent transport in a dynamically disordered medium, with application to polymer solid electrolytes[J]. PhyRev, 1985, B31(6): 3939-3947. |
| [24] | Siun H Y, Sohn H J, Yamamoto O, et al. Composite polymer electrolytes with improved lithium metal electrode interfacial properties (I): Electrochemical properties of dry PEO-LiX systems [J]. J Electrochem Soc, 1998, 145(12):4126-4132. |
| [25] | Wu H D, Wu I D, Chang FC. The interaction behavior of polymer electrolytes composed of poly (Vinyl pyrrolidone)and lithium perchlorate (LiClO4)[J]. Polymer, 2001, 42(2): 555-562. |
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